JP2661241B2 - Disinfectant and disinfectant resin composition containing ethylene copolymer as active ingredient - Google Patents

Description

The present invention relates to a bactericide and a bactericidal resin composition containing an ethylene copolymer having bactericidal activity as an active ingredient.

<Conventional technology> As a method for imparting bactericidal properties to resins, resin molded articles, textiles, paper products, etc., there are methods of mixing an organic chemical with a resin, and metals having bactericidal activity such as copper, silver, and zinc. A method of kneading a compound or the like is performed, and a method of processing into a fiber or the like and then treating with a drug is also available. (JP 62
JP-184126, JP-A-62-250277, JP-A-59-
No. 66578, JP-A-59-164342). As a method of retaining a metal compound, a method of retaining bactericidal metal ions in inorganic solid particles having ion exchange ability such as zeolite and kneading the particles with a resin (Japanese Patent Laid-Open No. 59-133235) No., JP-A-62-195037,
JP-A-62-195038) and the like have been proposed.

<Problems to be Solved by the Invention> As described above, in a method of mixing an organic drug with a resin, there are many problems in the thermal stability of the drug, the toxicity and harmfulness of the drug, and the durability is also high. Often not enough.
Regarding the method of containing a metal ion having a bactericidal action, simply kneading into a resin often causes dropout during use, and there is a problem in the persistence of the effect. As a method of improving this, a method of retaining metal ions in inorganic solid particles having ion exchange capacity such as zeolite is also used. It is necessary to make the diameter fine, which is expensive, and there is a problem in dispersibility at the time of kneading with a resin.

<Means for Solving the Problems> The present inventors have conducted intensive studies in order to solve such conventional problems, and as a result, it has been found that a copolymer of ethylene and a dialkylaminoalkylacrylamide comonomer has excellent bactericidal activity. It has been found that the present invention has been achieved. That is, in the present invention, ethylene is contained in an amount of 40 to 95% by weight, [Wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ and R ₃ are the same or different and represent an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 2 to 5]. ] 5 to 60% by weight of one or more dialkylaminoalkylacrylamide comonomer represented by the formula and 0 to 20% by weight of another one or more ethylenically unsaturated comonomer, and a number average Molecular weight 5000-5000
An object of the present invention is to provide a bactericide containing an ethylene copolymer which is 0 as an active ingredient.

Further, an aqueous dispersion of a chaotic polymer obtained by converting the above ethylene copolymer into a quaternary salt with hydrochloric acid in water and then adding an epihalohydrin-based compound is also included in the fungicide of the present invention.

Further, the above-mentioned ethylene copolymer containing a metal ion is also included in the bactericide of the present invention.

The ethylene copolymer of the present invention and the one containing metal ions therein, or the aqueous dispersion of the ethylene copolymer's chaotic polymer, the following plant diseases and industrially harmful bacteria that can be controlled include: Diseases can be raised but are not particularly limited to these bacteria.

Rice blast (Pyricularia oryzae), sesame rot (Cochlioboclus miyabeanus), sheath blight (Rhizoctonia)
solani), frog seedling disease (Gibberella fujikuroi), wheat scab (Gibberella zeae), snow rot (Typhula sp., M)
icronectriella nivalis, eye spot disease (Pseudocercospore)
lla herpotrichoides), scald disease (Rhynchosporium seca)
lis), leaf blight (Septoria tritici), leaf spot (Pyrenop)
hora graminea), Fusarium wilt (Leptosphaeria nodorum),
Citrus black spot (Diaporthe citri), scab (Els)
inoe fawcetti), green mold (Penicillium digitatum, P)
enicillium italicum, canker (Xanthomonas cit)
ri), apple monilinia disease (Sclerotinia mali), rot disease (Valsa mali), spot leaf rot (Alternaria mal)
i), scab (Venturia inaequalis), root canker (Agrobacterium tumefacien), pear scab (Ventur
ia nashicola), black spot (Alternaria kikuchiana),
Scab (Gymnosporangium haraeanum), peach scab (Sclertinia cinerea), scab (Cladosporium carpo)
philum), Phomopsis sp., grape black rot (Elsinoe ampelina), late rot (Glomer)
ella cingulata, oyster anthracnose (Gloeosporium kak
i), deciduous disease (Cercospora kaki, Mycosphaerella nawa)
e), cucumber anthracnose (Colletotrichum lagenarium),
Vine blight (Mycosphaerella melonis), spot bacterial disease (Ps
eudomonas lachrymans, tomato and ring spot (Alternaria)
solani), leaf mold (Cladosporium fulvum), eggplant brown spot (Phomopsis vexans), black spot on cruciferous vegetables (Alternaria japonica), white spot (Cercosporella bra)
ssicae), green onion rust (Puccinia allii), spring rot fungus (Pseudomonas syringae), soft rot (Erwinia cartovor)
a), soybean purpura (Cercospora kikuchii), black spot (Elsinoe glycines), black spot (Diaporthe phascolo)
rum var.sojae), bean anthracnose (Colletotrichum)
lindemuthianum), Peanut black spot (Mycosphaerel)
la personotum), brown spot (Cercospora arachidicol)
a), potato summer blight (Alternaria solani), tea net blight (Exobasidium reticulatum), white scab (Els
inoe leucospila, tobacco scab (Alternaria long)
ipes), Anthracnose (Colletotrichum tabacum), Sugar beet brown spot (Cercospora beticola), Carrot black spot (A
lternaria radicina, rose scab (Diplocarpon ro)
sae), chrysanthemum spot of chrysanthemum (Septoria chrysanthemiindic)
i), gray mold of various crops (Botrytis cinerea),
Sclerotinia sclerotiorum, seedling blight (Rhiz
octonia solani, pythium sp.), Aspergillus (As)
pergillus sp.), ketomium bacteria (Chaetomium sp.),
Cladosporium sp., Staphylococcus aureus, Escherichia coli (Escheri)
chia coli), Rhizopus sp., Aureobasidium sp., Mucor sp., Penicillium sp.,
Bacillus sp., Enterobacter sp.
terobacter sp.), Pseudomonas s.
p.), Saccharomyces sp., Candida sp. Fusarium moniliforme (F
usarium moniliforme) Trichoderma (Tricoderma s)
p.).

Accordingly, the ethylene copolymer used in the present invention and the one containing metal ions therein, or the aqueous dispersion of the cationic polymer of the ethylene copolymer, a fungicide for plants or seeds, wood, bamboo products, Non-medical products such as textile products, paper products, cosmetics, glasses, paints, synthetic resins, harmful bacteria-killing agents for industrial products, other sanitary processing agents, detergents or preservatives, slime control agents, food preservatives, etc. It can be used as an active ingredient of a fungicide.

There is no particular limitation on the method for producing the ethylene copolymer, but a so-called high-pressure polyethylene polymerization process is generally applied. That is, ethylene and acrylamide-based comonomer are mixed in the presence of a radical polymerization initiator for 500 minutes.
A method of copolymerizing under a polymerization pressure of 30003000 kg / cm ² and a polymerization temperature of 100 to 300 ° C. is used. Further, as a polymerization system, a batch system, a semi-continuous system, a continuous system, or the like can be employed, but a high-pressure continuous process is industrially advantageous.

In the production of the ethylene copolymer used in the present invention, a dialkylaminoalkylacrylamide comonomer is continuously and stably supplied to a high-pressure polymerization system by a pump. At least one other ethylenically unsaturated comonomer copolymerizable with ethylene can be combined as needed for the purpose of enhancing the properties. The polymerized units of the ethylenically unsaturated comonomer used in this case are from 0 to 20% by weight, preferably from 0 to 15% by weight. Preferred specific examples of the ethylenically unsaturated comonomer include, for example, methyl acrylate, ethyl acrylate, methyl methacrylate, vinyl acetate, dimethylaminoethyl methacrylate, and dimethylaminoethyl acrylate.

Preferable specific examples of the ziralkylaminoalkylacrylamide-based comonomer represented by the general formula [I] used as a raw material of the ethylene copolymer used in the present invention include, for example, dimethylaminoethylacrylamide, dimethylaminopropylacrylamide Dimethylaminobutylacrylamide, diethylaminoethylacrylamide, diethylaminopropylacrylamide, diethylaminobutylacrylamide, di-n-propylaminoethylacrylamide, di-n-propylaminopropylacrylamide, di-n-propylaminobutylacrylamide, N- (1, 1-dimethyl-3-
Dimethylaminopropyl) acrylamide, N- (2-
Methyl-3-dimethylaminopropyl) acrylamide and the like, and corresponding methacrylamide derivatives.

Particularly preferred comonomers include dimethylaminopropylacrylamide, diethylaminopropylacrylamide, dimethylaminoethylacrylamide, diethylaminoethylacrylamide and the corresponding methacrylamide.

The polymerization unit of the dialkylaminoalkylacrylamide comonomer of the ethylene copolymer used in the present invention is
It is 60 to 5% by weight, preferably 55 to 15% by weight. More preferably, it is 50 to 20% by weight.

Further, the number average molecular weight of the present ethylene copolymer is 5000 to 50000, preferably 8000 to 40,000 as a value obtained by comparing the peak count of GPC measured for a tetrahydrofuran solution with the peak of a standard polystyrene having a known molecular weight. is there. When the number average molecular weight is less than 5,000, the strength as a resin is weak, and it is difficult to uniformly knead with another resin, and when the number average molecular weight exceeds 50,000, kneading with another resin is also difficult. It is difficult to uniformly disperse.

The ethylene copolymer used in the present invention can be easily dissolved and fused to a thermoplastic resin, for example, a poly-α-olefin such as polyethylene or polypropylene, a chlorine-containing resin such as vinyl chloride, a polyester, or a polyamide. Thereby, a resin composition having bactericidal properties can be obtained.

When a resin composition in which the ethylene copolymer used in the present invention is mixed with another thermoplastic resin, the mixture is
0.1 to 50 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the thermoplastic resin. When the amount is less than 0.1 part by weight, the bactericidal activity is weak, and when the amount is more than 50 parts by weight, there are problems such that the original properties of the thermoplastic resin are lost or processability is reduced.

In addition, the present ethylene copolymer has a bactericidal activity, but further improves the bactericidal activity by absorbing or mixing and containing metal ions having a bactericidal activity such as silver, copper, and zinc. Can be held. The amount of the metal ion having a bactericidal property varies depending on the application, but is preferably 5% by weight or less. When the content is 5% by weight or more, there is a problem that the physical properties of the resin are changed.

As a method for containing metal ions, a thermoplastic resin and the present ene copolymer are melt-mixed to form a film, sheet,
It is easily achieved by processing into fibers, woven fabric, non-woven fabric, molded product, etc., and then immersing in a metal salt aqueous solution. In this case, depending on the use, by coexisting metal ions in the dyeing bath in the dyeing step, dyeing and metal ion absorption can be achieved at the same time, and the bactericidal treatment process can be simplified. Also, after absorbing the metal ions in the present ethylene polymer pellets, powder, etc., and dried,
The molding process may be performed by mixing with another resin.

In addition, the aqueous dispersion of the ethylene-based copolymer of the ethylene copolymer used in the present invention is, for example, 100 parts by weight of water, and 5 to 35 parts by weight of ethylene copolymer pellets,
Further, hydrochloric acid equivalent to 80 to 150 mol parts was added to 100 mol parts of the amino groups in the ethylene copolymer, and 60 to 100 ° C.
After stirring at a temperature of 30 to 120 minutes, the epihalohydrin compound is stirred at a temperature of 40 to 90 ° C. for 30 to 300 minutes at which 80 to 150 mol parts are added to 100 mol parts of amino groups in the ethylene copolymer. Is obtained by

When the ethylene copolymer used in the present invention and the one containing a metal ion or an aqueous dispersion of the ethylene copolymer's chaotic polymer are used as an active ingredient of a bactericide, a solid carrier, a liquid carrier , Surfactants,
Mix with other auxiliaries such as formulation, wettable powder, suspending agent,
It can be formulated into powders and aqueous suspensions and used.

The active ingredient content in the above formulation is usually 0.1 to 95 by weight
%, Preferably in the range of about 0.2-90%.

Examples of the solid carrier include kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn cob powder, walnut shell powder, urea, ammonium sulfate, and fine powders of synthetic hydrous silicon oxide and the like. Alternatively, a granular material can be used. Examples of the liquid carrier include water.

Surfactants used for emulsification, dispersion, wet spreading, etc. include alkyl sulfates, alkyl (aryl) sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkyl aryl ether phosphates, and naphthalene sulfones. Examples include anionic surfactants such as acid formalin condensate, and nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block copolymer, sorbitan fatty acid ester, and polyoxyethylene sorbitan fatty acid ester. Pharmaceutical adjuvants include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, carboxymethylcellulose (CMC), isopropyl acid phosphate (PAP) and the like.

In the case where the ethylene copolymer used in the present invention and the one containing a metal ion or the aqueous dispersion of a chaotic polymer of the copolymer are used as an active ingredient of a bactericide, the above-mentioned preparations may be used. , Liquid, emulsion, suspension, paste, granular, powdery, film, porous film, sheet, fiber, molded product, other forms alone or in combination with carrier such as paper, plastic inorganic plate, impregnated paper, paper diaper It can be used for, for example, wallpaper, packaging materials such as clothing and food, air filters, serts, building material boards or anti-mold paints.

Further, the ethylene copolymer used in the present invention,
Those containing metal ions are various thermoplastic resins, for example, poly-α-olefins such as polyethylene and polypropylene, and chlorine-containing resins such as vinyl chloride,
By processing after the resin composition is melt-mixed with polyester, polyamide, etc., films, seals,
It can be a molded article, fiber, or the like. Film products include packaging films, garbage films, etc., sheets as wallpaper, etc., and molded products, such as bathroom products, washing machines, kitchen and other puddle products. And a resin product having bactericidal properties.

Poly-α such as polyethylene and polypropylene
-Fiber products by mixing and spinning with olefins, polyesters and the like, or poly-α-olefin fibers, polyester fibers, polyamide fibers, acrylic fibers, fibers containing the ethylene copolymer of the present invention and natural fibers and the like. Can be used as a deodorant and antibacterial clothing such as deodorant socks and a net product such as a fish net.

Further, the ethylene copolymer according to the present invention is processed into a composite yarn such as a core-sheath type or a parallel type made by combining with a polypropylene resin, a polyethylene resin, a polyamide resin, and the like, and a woven fabric, a nonwoven fabric, and the like made from the composite yarn. By doing so, for example, it can be used for various life-related materials such as air conditioner filters, sheets, futons, and sanitary materials.

<Examples> Hereinafter, the present invention will be described in more detail with reference examples, formulation examples, test examples, and examples, but the present invention is not limited thereto.

Reference Examples 1 to 8 As shown in Table 1, liquefied ethylene and dialkylaminoalkylacrylamide comonomer (80%) were used in a continuous autoclave type reactor having an internal volume of 2 liters.
% By weight of a methanol solution), an ethylenically unsaturated comonomer, tertiary butyl peroxypivalate (as a 2% by weight n-heptane solution) as a polymerization initiator, and methylcyclohexane as a chain transfer agent. Ethylene copolymers [EC-1] to [EC-8] were produced at a pressure of 1700 to 1900 kg / cm ² and a polymerization temperature of 170 to 190 ° C.

Melt index of the obtained ethylene copolymer (JISK-6760,1
90 ° C), the copolymerization amount of dimethylaminopropylacrylamide determined by elemental analysis, and GP compared with a standard polystyrene sample (Toyo Soda Co., Ltd.) whose molecular weight is known.
The number average molecular weight determined by the method C was as shown in Table 1.

Reference Examples 9 to 12 In a 1000 ml glass flask, 360 g of water, 100 g of an ethylene copolymer in the form of pellets of ethylene and dialkylaminoalkylacrylamide comonomer, and 36% hydrochloric acid (1.0 to 1.0 mole ratio with respect to the amino groups of the copolymer) (Hydrochloric acid equivalent to 1.3), and the temperature is raised from room temperature to 100 ° C with stirring for 30 minutes.
Stirring was continued at reflux at 60 ° C. for 60 minutes. The pellets were disintegrated to form a slurry-like viscous solid-liquid mixture. Subsequently, after cooling to 80 ° C. with stirring, epichlorohydrin (epichlorohydrin corresponding to a molar ratio of 1.0 to 1.5 with respect to the amino group of the copolymer) is added dropwise over 30 minutes, and
By continuing to stir at 80 ° C. for 270 minutes, the aqueous dispersions of the light-brown, homogeneous chaotic polymer [s-1] to [s-
4] was obtained. The pH (25 ° C.), viscosity (25 ° C.), and solid content of the water dispersion after heating with hot air at 100 ° C. and remaining after water evaporation were as shown in Table 2.

Reference column 13 Using the same apparatus as in Reference example 1, liquefied ethylene, dimethylaminoethyl methacrylate as a comonomer, and tertiary butyl peroxypivalate (2
% By weight of N-heptane solution), and an ethylene copolymer was produced at a polymerization pressure of 1900 kg / cm ² and a polymerization temperature of 170 ° C. Melt index of the obtained ethylene copolymer (JIS
K-6760, 190 ° C.) was 290 g / 10 minutes, and the copolymerization amount of dimethylaminoethyl methacrylate obtained by elemental analysis was 43% by weight (12 mol%).

Next, formulation examples are shown. In addition, the ethylene copolymer according to the present invention is shown by the trial production number of the reference example in Table 1. Parts represent parts by weight.

Formulation Example 1 Ethylene copolymer (EC-1, EC) produced in Reference Examples 1 to 4.
-2, EC-3, EC-4) each obtained by freeze-grinding, 10 parts by weight of a resin powder having an average particle diameter of 100 μm, 3 parts of calcium ligninsulfonate, 2 parts of sodium lauryl sulfate 2
Parts, 45 parts of synthetic hydrous silicon oxide and 40 parts of kaolin clay are mixed well, and then EC-1 10% wettable powder, EC-2 10% wettable powder, EC-3 10% wettable powder and EC-410 are mixed. % Wettable powder was obtained.

Formulation Example 2 Ethylene copolymer (EC-5, EC) produced in Reference Examples 5 to 8
-6, EC-7 and EC-8) were mixed with 2 parts by weight of a fat powder having an average particle size of 100 μm each obtained by freeze-grinding with 88 parts of kaolin clay and 10 parts of talc, respectively.
% Powder, EC-6 2% powder, EC-7 2% powder and EC
-8 2% powder was obtained.

Next, test examples show that the ethylene copolymer and the aqueous dispersion of the cationic polymer according to the present invention are useful for harmful microorganisms.

Test Example 1 Bactericidal Spectrum against Harmful Bacteria EC-1 10% wettable powder, EC-4 10% wettable powder and the quatin of Reference Example 9 so that the potato / sucrose (PSA) medium had an active ingredient concentration of 10,000 ppm. Each of the aqueous dispersions of the water-soluble polymers was mixed with each other, poured into a 9 cm-diameter dish, and solidified. Thereafter, bacteria as a suspension or filamentous fungi as a spore suspension or a bacterial disk were inoculated into the center of the agar plate and cultured at 25 ° C.

The growth condition of the bacteria was observed, and the growth inhibitory effect of each test agent was examined. The results are shown in Table 3. The growth inhibitory effect was represented by the following index.

Index 4: Completely inhibits bacterial growth Index 3: Inhibits bacterial growth by 90% or more Index 2: Inhibits bacterial growth by 60-89% Index 1: Inhibits bacterial growth by 60% or less Test Example 2 Contact-Type Bactericidal Test The bactericidal activity under the condition where the frequency of direct contact of the microorganism with the aqueous dispersion of the ethylene copolymer and the cationic polymer thereof according to the present invention was examined using a liquid medium. The results are shown in Table 4.

Test bacteria: Spring rot fungus (Pseudomonas syringae) Medium: Polypeptone 2 g, glucose 5 g and water 1
Medium (hereinafter referred to as “PG medium”) Method: Test samples (EC-2, EC-3, EC-5, EC-6, EC-7,
EC-8, S-2, S-3, S-4) was suspended as a water suspension in a PG medium to a predetermined concentration shown in Table 4, and then the bacterial concentration of the test bacteria was measured. Was inoculated at 10 ⁶ cells / ml. Thereafter, the cells were cultured for about 20 hours using a shaking incubator under the condition of 27 ° C., and the growth inhibition of the bacteria was measured by a spectrophotometer.

Reference Examples 14 to 20 Copolymers shown in Table 5 were produced in the same manner as in Reference Examples 1 to 8.

Example 1 In the extruder (L / D = 20) of 300 mmφ, A shown in Table 5 was used.
To E and the various thermoplastic resins shown in Table 6 were kneaded to obtain 5 kg of pellets. The obtained pellet was placed on the tip of a 25 mmφ extruder (L / D = 15) with a hole diameter of 0.8 mm 12
It is fed to a spinning machine equipped with a hole nozzle, melt-spun at an extrusion rate of 1 kg / hr and a take-up speed of 450 m / min, then run on a hot plate and stretched three times to obtain a 10 denier / filament multifilament. Sample was obtained. The results are shown in Table 6.

Example 2 10 g of the obtained fiber sample was immersed in 300 ml of various metal salt aqueous solutions shown in Table 7 and held at 60 ° C. for 30 minutes to adsorb metal ions.

After sufficiently washing with ion-exchanged water, it was dried at 50 ° C. for 6 hours. In addition, acid dye (Suminol fast Blue PR con
c, manufactured by Sumitomo Chemical Co., Ltd.)
Staining was performed at 30 ° C. for 30 minutes. In addition, yarns not absorbing metal were dyed in the same manner. Further, a part was repeatedly washed with a detergent solution (Kao Attack, 1 g /, 50 ° C., 10 minutes).

The metal ion content in each fiber after incineration of the fiber,
The substance was dissolved in an acid and measured by an atomic absorption method, but hardly eluted by washing with a detergent. The results are shown in Table 7.

Test Example 3: Fungicidal activity test against mold Using the stained samples shown in Table 7 as test samples, a fungicidal activity test against mold was performed as follows.

Test bacteria: Aspergillus niger, Chaetomium globosum, Aureobasidium pullulans, Penicilliuim citrinum, Cladosporium herbarum, Rhizopus ric Trichoderma (Tric
hoderma sp.) Method: Place 1 g of the test sample on a Petri dish, and use an inorganic salt solution (KH ₂ PO ₄ 0.7 g, K ₂ HPO ₄ 0.7 g MgSO ₄ 7H ₂ O 0.7 g, NH ₄ NO ₃ 1.0 g,
0.005 g of NaCl, 0.001 g of MnSO ₄ 7H ₂ O, 0.005 g of FeSO ₄ 7H ₂ O, ZnSO ₄
A spore solution of the bacteria suspended in 7H ₂ O 0.002 g, water 1) was spray-inoculated. Thereafter, the cells were cultured for one month under the condition of high temperature and 27 ° C., and the degree of bacterial growth was observed and evaluated according to the following criteria.

+++: Growth of bacteria is observed in 1/2 or more of the sample. ++: Growth of bacteria is observed in 1/4 to 1/2 of the sample. +: Growth of approximately 1/4 of the sample is observed. Bacterial growth was slightly observed in the sample.-: No bacteria were observed on the sample. The results are shown in Table 8.

Test Example 4: Bacteria Bacteria Bacteria Bacteria Bacteria Bacteria Bacteria Bacteria Bacteria Bacteria Bacteria Bacteria Bacteria Bacteria Bacteria Bacteria Bacteria Bacteria Bacteria

Test bacteria: Spring rot fungus (Pseudomonas syringae) Medium: PG medium Polypeptone 2 g Glucose 5 g Water 1 Method: After suspending the test sample to a predetermined concentration in PG medium, the test bacteria are concentrated at 10 ⁶ Inoculation was performed so that the number of cells / ml was reached. Then, using a shaking incubator at 27 ° C for about 20 hours
Cultured for hours. This culture solution was filtered using filter paper, and the turbidity of the filtrate was measured using a spectrophotometer, and the degree of bacterial growth was investigated.

 The results are shown in Table 9.

Example 3 Ethylene copolymers B, F and G shown in Table 5 and various thermoplastic resins shown in Table 10 were kneaded with a 30 mmφ extruder to obtain 1 kg each of pellets.

Each kneaded pellet was cut out by a hot press into a pressed sheet having a thickness of 0.5 mm and a size of 5 cm × 5 cm. The press sheet was immersed in 300 ml of a copper sulfate solution containing 100 ppm of copper ions at 60 ° C. for 3 hours, and then washed with ion-exchanged water 1 for 5 minutes. Furthermore, what was dried at 60 ° C. for 5 hours with a hot air drier was used as a test piece.

Test Example 5: Fungicidal test against mold A fungicidal test against mold was performed in the same manner as in Test Example 3, except that the test piece prepared in Example 3 was used as a test sample.

The results are shown in Table 10. Comparative Test Example 2 Pellets obtained by kneading the thermoplastic resins shown in Table 10 with an extruder having a diameter of 300 mm were hot pressed to obtain a pressed sheet having a thickness of 0.5 mm. Using this as a test piece, the same bactericidal test for fungi as in Test Example 5 was performed. The results are shown in Table 10.

<Effect of the Invention> The germicidal agent and the germicidal resin composition of the present invention exhibit excellent effects against various harmful bacteria, and therefore, as an active ingredient of the germicidal agent, furthermore, fungicide, antifouling and antibacterial. It can be used for various applications such as various kinds of resin products having properties.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Koichiro Asao 2- 10-1 Tsukahara, Takatsuki-shi, Osaka Sumitomo Chemical Industries Co., Ltd. (72) Inventor Makoto Fujimura 4-2-1 Takashi Takarazuka-shi, Hyogo Sumitomo Within Chemical Industry Co., Ltd. (72) Inventor Shigeo Yamamoto 4-2-1 Takashi, Takarazuka-shi, Hyogo Prefecture Sumitomo Chemical Industry Co., Ltd. (72) Inventor Tomohiro Teramae 4-2-1 Takashi Takarazuka-shi, Hyogo Prefecture Sumitomo Chemical Industries Co., Ltd.

Claims (8)

(57) [Claims] (1) 40 to 95% by weight of ethylene, represented by the general formula [I]: [Wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ and R ₃ are the same or different and represent an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 2 to 5]. ] 5 to 60% by weight of one or more dialkylaminoalkylacrylamide comonomer represented by the formula and 1 to 20% by weight of another one or more ethylenically unsaturated comonomer, and a number average Molecular weight 5000-5000
A disinfectant characterized by containing as an active ingredient having an ethylene copolymer being 0. 2. An aqueous dispersion of a chaotic polymer obtained by subjecting the ethylene copolymer according to claim 1 to a quaternary salt with hydrochloric acid in water and then subjecting the ethylene copolymer to an addition reaction with an epihalohydrin compound as an active ingredient. A fungicide characterized by containing. 3. An ethylene content of 40 to 95% by weight of the general formula [I] [Wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ and R ₃ are the same or different and represent an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 2 to 5]. ] 5 to 60% by weight of one or more dialkylaminoalkylacrylamide comonomer represented by the formula and 0 to 20% by weight of another one or more ethylenically unsaturated comonomer, and a number average Molecular weight 5000-5000
A bactericidal property characterized in that a metal ion is contained in the ethylene copolymer which is 0. 4. The dialkylaminoalkylacrylamide comonomer is dimethylaminopropylacrylamide, diethylaminopropylacrylamide, dimethylaminoethylacrylamide, diethylaminoethylacrylamide, dimethylaminopropylmethacrylamide, diethylaminopropylmethacrylamide, dimethylaminoethylmethacrylamide, and diethylaminoethyl. 4. The fungicide according to claim 1, wherein the fungicide is at least one member selected from the group consisting of methacrylamide. 5. The disinfectant according to claim 3, wherein the metal ion is at least one of silver ion, copper ion and zinc ion. 6. An ethylene content of 40 to 95% by weight based on 100 parts by weight of the thermoplastic resin, [Wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ and R ₃ are the same or different and represent an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 2 to 5]. ] 5 to 60% by weight of one or more dialkylaminoalkylacrylamide comonomer represented by the formula and 0 to 20% by weight of another one or more ethylenically unsaturated comonomer, and a number average Molecular weight 5000-5000
A bactericidal resin composition obtained by melting and mixing 0.1 to 50 parts by weight of an ethylene copolymer which is 0. 7. Ethylene is 40 to 95% by weight based on 100 parts by weight of the thermoplastic resin, and the general formula [I] [Wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ and R ₃ are the same or different and represent an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 2 to 5]. ] 5 to 60% by weight of one or more dialkylaminoalkylacrylamide comonomer represented by the formula and 0 to 20% by weight of another one or more ethylenically unsaturated comonomer, and a number average Molecular weight 5000-5000
A bactericidal resin composition comprising 0.1 to 50 parts by weight of an ethylene copolymer which is 0 and a metal ion. 8. A sterilization method using the disinfectant according to claim 1, 2, or 3.